N-methoxyl formamide-orientated method for synthesizing ferrocene and pyridone derivative

Abstract

The invention discloses an N-methoxyl formamide-orientated method for synthesizing a ferrocene and pyridone derivative. According to the method, under the conditions that palladium acetate is taken as a catalyst, copper acetate is taken as a catalyst promoter and quaternary ammonium salt and alkali are taken as additives, an N-methoxyl ferrocene and [c] pyridine-2(1H)-ketone derivative is obtained by carrying out a cyclization reaction on N-methoxyl ferrocene formamide and alkyne. The method adopts an N-methoxyl formamide-orientated carbon-hydrogen bond and nitrogen-hydrogen bond double-activation reaction to synthesize the N-methoxyl ferrocene and [c] pyridine-2(1H)-ketone derivative in one step. The organometallic condensed heterocyclic compounds are unique in structure, thus being hard to prepare by a conventional method; the method provided by the invention has the characteristics of being easy in obtaining of raw materials and mild in reaction conditions, not needing the protection of inert gas, being high in synthetic yield, and the like; therefore, a new way is provided for the synthesis of novel ferrocene and heterocyclic compounds, and the method has an important significance for expanding the application of the compounds in the fields such as medicinal chemistry, material chemistry, catalysts and the like.

Description

technical field

[0001] The present invention relates to a ferrocenyl pyridone condensed heterocyclic compound and a synthesis method thereof, in particular to a N-methoxyferrocene[c]pyridin-2(1H)-one derivative and its synthesis method. Background technique

[0002] Heterocyclic compounds are a class of cyclic organic compounds containing heteroatoms, most of which have important biological activities. Various heterocyclic structures are widely found in natural products and chemical molecular structures such as drugs, pesticides, herbicides, and dyes ( (a) MichaelJ.P.Nat.Prod.Rep.,2008,25,139.(b)MichaelJ.P.Nat.Prod.Rep.,2007,24,191.(c)MichaelJ.P.Nat.Prod.Rep., 2005, 22, 603.). Therefore, the research on heterocyclic compounds, especially the research on the synthesis methodology of fused heterocyclic compounds has always been favored.

[0003] Ferrocene and its derivatives are a very important class of organometallic compounds, and their core skeletons frequently appear i...

Examples

Embodiment 1

[0033] N-methoxyferrocenecarboxamide (0.1036g, 0.4mmol), diphenylacetylene (0.1424g, 0.8mmol), palladium acetate (0.0100g, 0.044mmol), sodium acetate (0.0410g, 0.5mmol), A mixture of CTAB (0.0292g, 0.08mmol) and toluene (2mL) was reacted at 65°C for 12 hours. The reaction mixture was cooled to room temperature, 5 mL of water was added, and then extracted with ethyl acetate, the extract was washed with saturated brine, the organic phase was dried over anhydrous magnesium sulfate, and the filtrate was evaporated under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, eluent: ethyl acetate / petroleum ether=1:1, v / v, R f =0.5) to obtain a red solid, N-methoxy-5,6-diphenylferroceno[c]pyridin-2(1H)-one, with a yield of 92%, m.p.177°C (dec.).

[0034] HR-MS(ESI)(m / z): Calcd.forC 26 h 21 FeNO 2 [M] + 435.0922,Found:435.0921.

[0035] 1 HNMR (300MHz, CDCl 3 ):δ7.24-7.21(m,10H),5.32(d,1H,J=...

Embodiment 2

[0037] N-methoxyferrocenecarboxamide (0.1036g, 0.4mmol), diphenylacetylene (0.1424g, 0.8mmol), palladium acetate (0.0100g, 0.044mmol), copper acetate (0.0020g, 0.011mmol), A mixture of sodium acetate (0.0410g, 0.5mmol), CTAB (0.0292g, 0.08mmol) and toluene (2mL) was reacted at 65°C for 8 hours. The reaction mixture was cooled to room temperature, 5 mL of water was added, and then extracted with ethyl acetate, the extract was washed with saturated brine, the organic phase was dried over anhydrous magnesium sulfate, and the filtrate was evaporated under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, eluent: ethyl acetate / petroleum ether=1:1, v / v, R f =0.5) to obtain a red solid, N-methoxy-5,6-diphenylferroceno[c]pyridin-2(1H)-one, with a yield of 93%, m.p.177°C (dec.).

[0038] HR-MS(ESI)(m / z): Calcd.forC 26 h 21 FeNO 2 [M] + 435.0922,Found:435.0921.

[0039] 1 HNMR (300MHz, CDCl...

Embodiment 3

[0041] N-methoxyferrocenecarboxamide (0.1036g, 0.4mmol), 1-phenyl-2-(4-nitrophenyl) acetylene (0.1785g, 0.8mmol), palladium acetate (0.0100g, 0.044mmol ), copper acetate (0.0020g, 0.011mmol), sodium acetate (0.0410g, 0.5mmol), CTAB (0.0292g, 0.08mmol) and acetonitrile (2mL) were reacted at 65°C for 7 hours. After the reaction mixture was cooled, 5 mL of water was added first, and then extracted with ethyl acetate. The extract was washed with saturated brine, and the organic phase was dried with anhydrous magnesium sulfate. The filtrate was distilled off the solvent under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, eluent: ethyl acetate / petroleum ether=1:1, v / v, R f =0.5) to obtain a dark red solid, N-methoxy-6-phenyl-5-(4-nitrophenyl)ferrocene[c]pyridin-2(1H)-one, yield 98%, m.p.165°C (dec.).

[0042] HR-MS(ESI)(m / z): Calcd.forC 26 h 20 FeN 2 o 4 [M+H] + 481.0851, Found: 481...

technical field

[0001] The present invention relates to a ferrocenyl pyridone condensed heterocyclic compound and a synthesis method thereof, in particular to a N-methoxyferrocene[c]pyridin-2(1H)-one derivative and its synthesis method. Background technique

[0002] Heterocyclic compounds are a class of cyclic organic compounds containing heteroatoms, most of which have important biological activities. Various heterocyclic structures are widely found in natural products and chemical molecular structures such as drugs, pesticides, herbicides, and dyes ( (a) MichaelJ.P.Nat.Prod.Rep.,2008,25,139.(b)MichaelJ.P.Nat.Prod.Rep.,2007,24,191.(c)MichaelJ.P.Nat.Prod.Rep., 2005, 22, 603.). Therefore, the research on heterocyclic compounds, especially the research on the synthesis methodology of fused heterocyclic compounds has always been favored.

[0003] Ferrocene and its derivatives are a very important class of organometallic compounds, and their core skeletons frequently appear i...

Examples

Embodiment 1

[0033] N-methoxyferrocenecarboxamide (0.1036g, 0.4mmol), diphenylacetylene (0.1424g, 0.8mmol), palladium acetate (0.0100g, 0.044mmol), sodium acetate (0.0410g, 0.5mmol), A mixture of CTAB (0.0292g, 0.08mmol) and toluene (2mL) was reacted at 65°C for 12 hours. The reaction mixture was cooled to room temperature, 5 mL of water was added, and then extracted with ethyl acetate, the extract was washed with saturated brine, the organic phase was dried over anhydrous magnesium sulfate, and the filtrate was evaporated under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, eluent: ethyl acetate / petroleum ether=1:1, v / v, R f =0.5) to obtain a red solid, N-methoxy-5,6-diphenylferroceno[c]pyridin-2(1H)-one, with a yield of 92%, m.p.177°C (dec.).

[0034] HR-MS(ESI)(m / z): Calcd.forC 26 h 21 FeNO 2 [M] + 435.0922,Found:435.0921.

[0035] 1 HNMR (300MHz, CDCl 3 ):δ7.24-7.21(m,10H),5.32(d,1H,J=...

Embodiment 2

[0037] N-methoxyferrocenecarboxamide (0.1036g, 0.4mmol), diphenylacetylene (0.1424g, 0.8mmol), palladium acetate (0.0100g, 0.044mmol), copper acetate (0.0020g, 0.011mmol), A mixture of sodium acetate (0.0410g, 0.5mmol), CTAB (0.0292g, 0.08mmol) and toluene (2mL) was reacted at 65°C for 8 hours. The reaction mixture was cooled to room temperature, 5 mL of water was added, and then extracted with ethyl acetate, the extract was washed with saturated brine, the organic phase was dried over anhydrous magnesium sulfate, and the filtrate was evaporated under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, eluent: ethyl acetate / petroleum ether=1:1, v / v, R f =0.5) to obtain a red solid, N-methoxy-5,6-diphenylferroceno[c]pyridin-2(1H)-one, with a yield of 93%, m.p.177°C (dec.).

[0038] HR-MS(ESI)(m / z): Calcd.forC 26 h 21 FeNO 2 [M] + 435.0922,Found:435.0921.

[0039] 1 HNMR (300MHz, CDCl...

Embodiment 3

[0041] N-methoxyferrocenecarboxamide (0.1036g, 0.4mmol), 1-phenyl-2-(4-nitrophenyl) acetylene (0.1785g, 0.8mmol), palladium acetate (0.0100g, 0.044mmol ), copper acetate (0.0020g, 0.011mmol), sodium acetate (0.0410g, 0.5mmol), CTAB (0.0292g, 0.08mmol) and acetonitrile (2mL) were reacted at 65°C for 7 hours. After the reaction mixture was cooled, 5 mL of water was added first, and then extracted with ethyl acetate. The extract was washed with saturated brine, and the organic phase was dried with anhydrous magnesium sulfate. The filtrate was distilled off the solvent under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography (silica gel: 200-300 mesh, eluent: ethyl acetate / petroleum ether=1:1, v / v, R f =0.5) to obtain a dark red solid, N-methoxy-6-phenyl-5-(4-nitrophenyl)ferrocene[c]pyridin-2(1H)-one, yield 98%, m.p.165°C (dec.).

[0042] HR-MS(ESI)(m / z): Calcd.forC 26 h 20 FeN 2 o 4 [M+H] + 481.0851, Found: 481...

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